Synthesis of carbinols



Jan- 8, 1952` P. VAN 'T SPIJKER ETAL 2,581,988

SYNTHESIS OF CARBINOLS Filed Oct. 17, 1950 R v mu m P N ms O T.T T N .T y ,55. .l @mn u TA NMm..` T E V m NNI-COU MZON Patented Jan. 8, 1952 SYNTHESIS yOF CARBINOLS Peter van t Spijker, The Hague, and Marius t Hart, Amsterdam, Netherlands, assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware f g f Application October 17, 1950, Serial No, 190,528

In thev Netherlands J anuary 26, 1950 1 claim. (cl. 26o- 638) This invention relates to an' improvement in the synthesis of carbinols by the catalyzed addition of carbon monoxide and hydrogen to olefins or other compounds containing at least one olenic double bond, which process is generally known as the OXO-process. More specifically, this invention relates to an improvement in the synthesis of carbinols by the 0x0-process of the type in which the synthesis is carried out in steps and the catalyst is carried through the separate g reaction zones as a slurry in the liquid reaction mixture.

The reaction conditions, reactants, catalysts and such particulars applicable in the Oxoprocess are well known and described in the art. The method of operation in which the synthesis is carried out in steps and the catalyst is carried through the reaction Zones in suspension in the liquid reaction mixture is also well known and' described in the art.

In the multi-step 0x0-process the olenic reactant, e. g. an olen polymer or an olenic concentrate from a cracked hydrocarbon fraction, is reacted with carbon monoxide and hydrogen in a first step or stage to give a product which con-f sists largely of aldehydic products along with minor amounts of higher boiling oxygenated products (thick oil), carbinol, unreacted olefin, diluents, soluble cobalt compounds and suspended catalyst. This rst stage is called the carbonylation stage since it is in this stage that the addition of the carbon monoxide takes place along with the addition of part of the hydrogen.

As stated, the product from the carbonylation stage contains dissolved cobalt. This dissolved.

'dehydic intermediate products are converted to thecarbinols. The product of this stage consists largely of the desired carbinols with lesser amounts of higher boiling oxygenated products (thick oil) diluents and suspended catalyst. This product is worked upto recover the desired carbinol in the desired degree of purity and this is effected at least in part by .separating the suspended catalyst (usually by filtration) followed by fractional distillation.

The catalystused is cobalt, and it is generally and preferably used in conjunction with a powdered carrier material of which the diatomaceous earth known under the trade name Celite is a good example. Cobalt is an excellent catalyst for both the carbonylation and the subsequent hydrogenation, and, as described, it serves as the catalyst for both stages in the process.

The catalyst declines in effectiveness at a slow rate and, consequently, it is the practice to recycle the catalyst, after separation from the product, back to the carbonylation stage to effect synthesis of further amounts of product. The amount of catalyst required to be supplied with the feed is vrelatively small, e. g,`4% by weight based on the olefinic reactant feedi' .E Thus, in the typical operation ofthe process the catalyst filtered from the product is slurried in part of the feed or in a portion of the thick oil, and a small amount of the slurry sufficient to supply the required amount of cobalt is added to the carbonylation stage, usually in suspension in the olenic reactant.

However, the activity of the catalyst does decline slowly with use and, consequently, it is the practice to substantially continuously discard a minor portion (e. g. 10%) ofthe recycled catalyst and replace it with fresh catalyst. This is done in the obvious way which is to discard part of the iilter cake and add fresh catalyst at the point where the remaining portion of the filter cake is repulped preparatory to recycling it back to the carbonylation stage.

We have now found that the described usual method of maintaining the activity of the catalyst by replenishment with fresh catalyst is not the best way to operate the process. We have found that the processmay be improved if the fresh catalyst used for replenishment (replacement) is added at a point just preceding the hydrogenation stage. We have found that when the fresh catalyst is added at that point, rather.

than just before the carbonylation stage, the yield of product is improved and that this is due to a lesser formation of the undesired heavy by-products (thick oil).

The eifect of fresh catalyst upon the formation of thick oil is illustrated by the following data. The feed was a C6-C8 fraction containing 86% olens. The catalyst was Acobalt mounted on Celite and contained about 33% by weight cobalt. The catalyst was supplied to the carbonylation zone as a slurry in the feed (about 4% by weight). The carbonylation was carried "out in a baiiled vertical upflow reactor having two jacketed sections. Other conditions were constant and as follows:

`Pressure 200 atm.

Liquid hourly space velocity calculated on vboth reactor sections JOBl/lf/hr. Entrance "gas rate 1.5"`Stdm.3/sec. High pressure gas bleed 7 l04 Std. m.3/sec. Temperature:

Inlet 97C. y Bottom section 14S-160 C. gradient Top section 5%451'0.

Over Va period of 108 hourseoflcontinuous.operation fresh catalystwas supplied to the carbonylation zone; then over a period o 217 hours only recycled catalyst was supplied tolthecarbonylation zone. The results'are shown inthe following table:

Table VIt-wiube-mmed@them-althoughitherresh cata;- g lystfgave auslightlyfhigherfconversionand yield of loXygena-telfproductsf.the@proportion vof heavy oxygenatedfproductscthick oil) 1 wasV greatereland t the actual:productionf-oktheydesired- 4'alcohol was fless.

The process fof' thefrinvention: is illustrated 'by f the following non-limitingfexample--which 7is: dev kscribed r in conjunction vwith the-f1ow=diagram il- .lustrated .inthe accompanying fdrawing.

vExample In thisfexampleftheafeedfisobtainedby cracking parain wax-andseparating.fromthegproduct of. a Caz-Ca fractionihaving the. following comporjsition:

"Ce .percent by'weight '"48 Cmpercent by weight 40 .Ca `percent byu Weight "12 "Total olen'content ;;.percent 87 Sulfur 'do i 0:02

" The -c'atalystvis A'preparedLbyfprecipitating cobalt f `carbonate'on Cel-ite 1290-; followedlby reduction.' at 500 C. in afstr'ea-m'of hydrogenfandf contains -ap- 'f proximatelyil 'Coahdl-E-.f Celite.

i "The -gas-suppliedto the-Jcarbonylation'stage has the vfollowing:compositiorrinj perfcenteby volume:

Referring 'to` the"drawing;"the olenic :.feed' isintroducedl atV ajrateof I1` 3001'kg/hr. by `line. i Recycle hydrocarbon 'containing about 26% olens is introduced'pgby'lin 2;atV arate :of 390fkg`l/hr. (Recycle ratio of 03:1.) Agcatalyst"slurry'prej paredjby. slurryingj'the"catalyst separated. from thnalmpro'duct infa'po'rtiorfof thethick' oil 'to 4 a concentration of 25% by weight is introduced by line 3 at a rate of 3-0'? lig/hr. (about 4,5% catalyst by weight, based on the feed). Fresh synthesis gas is introduced by line 8 under a pres- 5 sureV of 200 atm. at a rate of 0.5 m/kg. of fresh olenic iced. :This gaseis addedto the recycle -.gas introduced-by line 4'laat au rate of'r0g75 m.3/kg. of fresh olenic feed. The mixture of reactants aand catalyst is then passed by line 5 to the car- 10;..bonylationreact0r S.

""'The carbonylation reactor is divided into three `sections gbybaiiers 9 and 9a, and each section is .providedG-'W h aelcoil-i, Illa and Mib-to allow -rindep'endent control of the temperature in each -lseetion ""T-heereactant mixture rst passes up .throughthe .lower or pretreating Zone maintained .-.jat a lomtemperature of about 110 C. The residencertime in the pretreating section may be,

for example, about 7 min. The pretreated mixture then passes upward into the carbonylation @pemex-'Which'. is main-tainedeat a-temperature of -about"-160 C11-lere the-carbonylationfreaction is initiatedfand-Lcarried :outff-The top .sectiongcalled the after treatingsection,--y is; maintaimed @ati a 25. lower@temperaturey e; gli-80? C. Y

' "Thereactionproductefrointhefcarbonyla-tion l 504'genat'on stage" isv passed'to theinjectorjbyine heaters-26 and"back intoithesdecobaltizer. The

- Vmixture of 'gasa-nd -deccbaltized product is super- "bottom of"the `decobaltizer Lthrough' a"nozzlef"2l Which vmixesU itrwith the' incoming (feed. It is essentialethat aihydrogen` pressurein thev heater 'a2 5' @be maintained fat'. about' "10J atm'. lor above. AIn

the case .'il1ustrat'ed,; a pressure AV'of'50ajtm- "is 50 maintained. The; gas 'is 'Withdrawn from -the decobaltizer byline" Z i The remaining'decobalted product- `Withdrawn byline22`is Vcool'edzand' then expanded into sepr arator 28. Released gas isV vented and'the slurry 6J is then passed tol amixmgtamfzs. 'Hereifresh Q maintain thecatalyst at'the.'desiredflevellpf 'activity, e., g.. 10% of thecatalystbeing circulated.

o throughthe preheater 30 to thehydrogena'tion at 150'atm. pressure `and"l'80"lC9200" C..by.fre"sh hydrogen added'. by 1ine'f32. 'Thefyhydrogen'ated product is cool'ed' andgjp'assed to 'ase-parator in the conventional manner.'"""Part of' the unused hydrogen may be Withdrawn by line 33 or recycled to the system. A part of the hydrogen is passed by line 25 to the injector 24 as described. The hydrogenated slurry is passed from the separator to a lter 34. The liquid product is Withdrawn by line 25 and may be Worked up in any Way desired. Part of the lter cake is Withdrawn from the system by line 36 and the remainder is recycled to the carbonylation zone. Thus, part of the catalyst is passed to the repulping tank 31 where it is mixed with lthick oil and the concentrated slurry is passed to the carbonylation zone by lines 3 and 5, as previously described.

When working in this manner, 0.937 ton of Cv-Cs alcohol may be obtained per ton of the olefnic feed.

We claim as our invention:

In a process for the synthesis of a carbinol by carbonylation using a cobalt catalyst which is passed in suspension in the reaction mixture through a rst canbonylation stage and a subsequent hydrogenation stage, the improved method of maintaining the activity of the catalyst at a desired level which comprises adding a quantity of fresh catalyst to the reaction mixture subsequent to said carbonylation stage and prior to said hydrogenation stage,separating suspended catalyst from the reaction mixture from said hydrogenation stage, withdrawing and discarding an amount of the separated catalyst equal to the quantity of said fresh catalyst added, and recycling the remainder of the catalyst to the carbonylation stage.

Y PETER vAN "r SPIJKER. MARIUS r HART.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,504,682 Harlan, Jr. Apr. 18, 1950 2,564,456 Vlugter et al. Aug. 14, 1951 

